Polymerization product of sulphur dioxide and allyl cyanide



as ethylene,

Patented Apr. 1940 PATENT OFFICE 2,198,936; POLYMERIZATION PRODUCT or SULPHUR DIOXIDE AND Frederick E. Frey and ville, Okla", and Louis H.

late of Bartlesville,

ALLYL QYANIDE Robert D. Show, Bartles- Fitch, Jr., deceased, 0kla., by First National Bank in Bartlesville, administrator, Bartlesville, 0kla., assignors to Phillips Petroleum Company, Bartlesville, Okla, a corporation of Delaware No Drawing'. Application September 6, 1938,

Serial No. 228,702

3 Claims.

This invention relates to the manufacture of m phur dioxide and having incorporatedin the molecule, radicals suchas the hydroxyl or carboxyl, capable of undergoing further reaction with suitable chemical agents.

Other objects will appear as more fully described.

Prior literature references to the reactions of S02 with unsaturated compounds are confined to the olefin and diolefin hydrocarbons. Mathews and Elder, British 11,635, 1914, claim the-reaction' of liquid S02 with oleflnic hydrocarbons, such propylene, and :butylenes in sunlight or ultraviolet light. De Bruin, Chem. Abs. 9,623 (1915) found that the conjugated diene, isoprene, when allowed to stand with liquid S02, forms a crystalline compound. Mathews and Strange, U. S. 1,196,259 (1916), react isoprene and other conjugated diolefins with S02 in the presence of halogen compounds such as HCl, iodine or acetyl chloride, which promote the formation of the crystallizable sulphoxide. Badlsche Aniline and Sodafabrik, German 236,386 (1911), Staudinger,

the invention is German 506,839 (1930), and Perkins, Canadian 329,043 (1933), disclose the reaction of S02 with olefins having conjugated double bonds. Leopold 0 Singer in French Patent No. 515,590 (1921) discloses a process for the production of lacquers, varnishes, etc., by reacting sulphurous acid with mineral oils. In thesereferences to the prior art, no mention is made of the reaction of S02 with unsaturated compounds other than simple olefins and con ugated dioleflns. Furthermore, since methods for the reaction of many of the simple are still unknown, it does from the previous disclooleflnic hydrocarbons not necessarily follow than simple olefins and conjugated diolefin hydrocarbons react with S02 to form high molecu- 50 lar weight polymers f a resinous nature.

sures that unsaturated compounds other than We have reacted the following materials with 'sulphur dioxide:

The unsaturated halogen derivatives, vinyl chloride and allyl chloride react readily with liquidSOz in the presence of a catalyst or in light. The vinyl chloride forms a white solid which is insoluble in S02, but which .can be molded by heat and pressure. The allyl chloride forms a water white, glassy product somewhat soluble in S02. After molding by heat and pressure, the resin exhibits high mechanical strength. The unsaturated alcohol, allyl alcohol, reacts readily with S02 in the presence of catalyst or light. The solld resinobtained has a very high tensile strength.

The unsaturated ether, allyl ethyl readily with S02 in the presence of catalyst or light. The solid resinous product can be molded by heat and pressure.

The olefin oxides, or inner ethers, ethylene oxide and propylene oxide react relatively more slowly with S02 in the presence of catalyst or light at temperatures up to 40 C. but preferably at about 0 C. The products are viscous fluids useful. as'softening agents, plasticizers, and solvents,

.Esters of acrylic acid react readily with S02 in the presence of light or catalyst to form products of desired properties. Ethyl acrylate reacts ether, reacts to form asoft, rubbery product soluble in S02.

and many organic solvents.

When S02 is passed into an unsaturated amine compound such as allylamine, the first energetic reaction is evidently between the -NH2 group and the S02. If after this reaction is complete, an excess of S02 is posed to light, a further reaction takes place, forming'a compound of high molecular weight.

Diallyl, a diolefln not having conjugated double bonds and consequently not being capable of undergoing 1-4 addition of S02, was found to react rapidly with S02 to form a white insoluble diflicultly fusible solid. The unsaturated aldehyde, acrolein,- reacts slowly with S02 in the presence of light or catalyst. The reaction can best be carried out at temperatures below atmospheric. The product is a solid insoluble in S02. I

The unsaturated acids, acrylic, allylacetic, and undecylenic react readily with S02 in the presence of a catalyst or light. The products are added and the mixture is exinsoluble'in excess S02. They are softer than the products obtained from olefinic hydrocarbons of the same number of carbon atoms, the product of undecylenic acid being very soft and pliable.

The acetylene derivatives, ethyl acetylene and phenyl acetylene, react with S0: in' the presence of light or a catalyst,

The acetylene polymers, vinyl acetylene, divinyl acetylene, and polydivinylacetylene, react slowly in liquid S02 in the light or in the presence of a catalyst to form an insoluble'brown solid.

The furane derivative, furfuryl alcohol, reacts with $02 in the light or in the presence of a catalyst. A jet black solid material which is practically insoluble and-can be molded only at high temperatures and pressures is formed.

Other compounds which we have converted to resins by reaction with $02 are: allyl cyanide, allyl isothiocyanate, allyl thiourea, and allyl urea.

Other materials which should react with S02 are: crotonyl alcohol, chloroprene, bromoprene, unsaturated vegetable oils such as tung oil, and partially chlorinated olefins such as the dichloride of diallyl.

In most cases we have found that the treatment of the unsaturated product to remove any absorbed oxygen and oxidation products prior to reaction is desirable. Although the reaction involves approximately equimolecular proportions of S02 and unsaturated compound, the reaction product usually removes excess S02 from the reaction phase in the absorbed or dissolved form. It is, therefore, generally desirable to'use more than the molecular equivalent of S02.

Any of the catalysts forthese reactions pre- V viously discovered and disclosed can be used, insofar as they are compatible with the unsaturated compound to be converted to resin.

Resinous products formed from mixtures of simple olefinic hydrocarbons and other unsaturated compounds appear to have properties which are generally intermediate between those formed from the individual constituents.

In many ways the production of resins from such compounds as unsaturated halogen derivatives, alcohols, ethers, esters, acids and aldehydes, or materials containing them, by reaction with S02 is highly desirable and advantageous. It would permit the production of resins having special properties; for example the allyl alcohol- S02 resin has unusually high tensile strength, while the undecylenic acid-S02 and ethyl acrylate-SOz resins are soft and rubbery. Then; too, a resin in which is tied up such a compound of multiple functions should be capable of further modification of properties by other chemical reactions after formation of the S02 complex. Apparently only the carbon to carbon double bond is involved in the resin reaction, leaving the other functional groups, such as hydroxyl or carboxyl, more or less free to undergo its characteristic re actions. Thus, an allyl alcohol resin or an acrylic acid resin might be esterified in the usual manner with acid anhydrides or alcohols, respectively, to produce resins with a wide range of properties. Still another advantage of the use of these compounds is that they can be used to modify the properties of resins from unsaturated hydrocarbons and S02. This may be accomplished in either of two ways; the unsaturated polyfunctional compound may be mixed with the nsaturated hydrocarbon and S02 before reaction, in which case opportunity is afforded for molecules of both types of unsaturated compounds to build into the same resin molecule; or the resins of the two types of compoundsmay be formed by reacting separately with S02, and then be blended in the desired proportions after reaction. I

We have produced useful resinous products by the reaction of 802' with unsaturated compounds other than simple olefinic hydrocarbons and conjugated diolefinic hydrocarbons, have blended the resins so obtained with resins formed by the reaction of S0: with simple olefins and/or diolefins in order to modify the properties of the latter and have also mixed such unsaturated compounds with the simple olefins and diolefins and reacted the mixture with $02 under the proper conditi ns.

The, ollowing examples will illustrate the process of the present invention:

I. Equal volumes of liquid S02 and allyl chloride are sealed in a glass tube and exposed to sunlight or artificial light, preferable of short wave length. After the reaction has gone to completion, as indicated by the conversion of the fluid reactants to a stiff gel, the excess S02 is allowed to evaporate, leaving a white solid resin.

As a variation of the above, suitable for larger scale operation, the mixture of S02 and allyl chloride isplaced in, a bomb or autoclave pro-' vided with a suitable source of internal illumination and the reaction is promoted photochemically.

II. Equal volumes of liquid soil and allyl alcohol are placed in a bomb or autoclave containing 0.010.1 per cent of silver nitrate, .or other suitable catalyst and. are allowed to react after thorough mixing. After the reaction has gone to completion, the excess S02 is allowed to escape and the solid resin is removed from the vessel.

111. To a mixture of 25 parts by weight of undecylenic acid and 75 parts of propylene was added somewhat more than twice its weight of liquid sulphur dioxide. After mixing, a catalyst solution consisting of 5% alcoholic lithium nitrate solution in ethyl alcohol was added at the rate of 2 per cent of the weight of the reaction mixture. The mixture was agitated while reaction was taking place. After completion of the reaction, the excess sulphur dioxide was removed. A resin having much better plasticity than that of propylene-sulphur dioxide resin was obtained. The product when molded also showed much less tendency to crack than the ordinary,

propylene sulphur dioxide resin.

IV. A mixture of 20 parts of propylene, 10 parts of methyl undecylenate and parts of sulphur dioxide was caused to react in a pressure vessel by the addition of 2 parts of 5% alcoholic lithium nitrate solution. The mixture was agitated during reaction. At the end of the reaction the excess sulphur dioxide was expelled We claim= v 1. The process of producing high molecular weight heteropolymeric products which comprises v3. The process of producing high molecular weight heteropolymeric products of sulphur dioxide and allyl cyanide which comprises reacting allyl cyanide with sulphur dioxide in the presence of an excess of the latter, and removing uncombined sulphur dioxide from the product of the reaction. 7

FIRST NATIONAL BANK v IN BARTLESVILLE. Administrator of the Estate of Louis H. Fitch, Jr.,

Deceased,

' By J. F. ,CRONIN,

Vice President. FREDERICK E. FREY. ROBERT D. SNOW. 

